DE2032417A1 - Process for the production of cement copper free of arsenic from acidic arsenic-containing solutions - Google Patents

Description

PA Γ f NTANWA · .. *. Fc 7 Q 3 C. AI 7

PROF. DR. DR. J. REIT 5TÖ TTER

DK.-ING. WOLFRAM BUNTE

DR. KARL GEORG LÖSCH

ι · '- ■.:> (! ■.', Ii -ClAUt-RuTf-A "JI .'-- 'iV ί- -.α =». ¹ >.' (■. ·!>

Munich, 3 α JUN11970 M / 11192

MONTECASINI EDISON S.P.A. 31, Foro Buonaparte, Milan (Italy)

Process for the production of cement copper free of arsenic from acidic arsenic-containing solutions

The present invention relates to a method of extraction from arsenic-free copper based on acidic solutions, which, in addition to copper ions, contain chlorine ions and arsenic.

In the purification process of iron minerals _(T pyrite ash, Pyrrhotitaschen, flotation concentrates and the like) by chlorinating roasting or by chlorinating volatilization be obtained solutions containing, among other things Elven, copper, zinc, lead, silver, gold and arsenic. These solutions are subjected to a series of treatments to separate the valuable components in the form of metals or oxides.

According to the classical hydrometallurgical process of Duisburger Kupferhütte is the first treatment in one

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Precipitation of copper together with gold and silver by means of a metal that is more electropositive than copper, such as iron or zinc. The term "precipitation" or "cementation" means the process in its main features, for example in Ullman's Encyclopedia of Industrial Chemistry, Volume 11 (I96o), Page 174, 185 to 18? is described.

The main disadvantages of this method are of various kinds. The main disadvantage is that starting from solutions containing arsenic a cement copper is obtained which is heavily contaminated by arsenic or at least has arsenic contents which are greater than the tolerance limit of 0.3% . In addition, highly toxic arsine develops in the course of the precipitation and high iron consumption occurs, according to the following reactions:

Cu ⁺⁺ + Pe »Cu + Pe ⁺⁺

2 Pe ⁺⁺⁺ + Pe $ 3 Pe ⁺⁺

2 H ⁺ + Pe -> H ₂ + Pe ⁺⁺

Ψ The above reactions all also lead to the formation of a considerable amount of Pe ⁺⁺ , which must then be removed from the solution in order to be able to recover the other metals or to be able to safely discard the solution.

ι In the German patent specification 1 127 597 a method is ^:

described, which partially overcomes this disadvantage and allows the j limitation of the iron consumption for the precipitation. According to this procedure, the copper is removed from the solutions .in Porm of copper-I-chloride duroh addition of finely divided

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ORIGINAL IMSPECTED

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metallic copper according to the reaction:

CuCl ₂ + Cu -> 2CuCl

failed.

Most of the CuCl formed in this way precipitates and is then separated and converted to metallic material according to various methods Refurbished copper. The remaining copper in the solution is then reduced to cement copper, which is used in the above Precipitation stage of the process is returned to the to reduce divalent copper.

Another method described in German patent specification 1 153 907 and used industrially consists in a reduction treatment of the divalent copper by means of SO ₂ and metallic copper. The separated CuCl is dechlorinated separately by adding lime, whereby copper-I-oxide is obtained, which can be processed directly on raw copper in the reduction furnace, while the remaining copper remaining in solution is also cemented.

These cuprous chloride processes only provide essentials Advantages if this Rupfer-I-chloride directly for the production of copper oxychloride, which in turn can be used as a fungicide and insecticide. if If this is not the case, then the Rupfer-I-chloride is an intermediate product, which still the use of metallic iron to achieve cement copper or the use of lime Requires to achieve copper-I-oxide. The main disadvantage in the spring case lies in the fact that the cement is copper or the CuCl due to the arsenic in the solution are contaminated.

One described in German Patent 1,222,683 another method overcomes this disadvantage by adding both

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the reduction phase of the "Ou to the Cm (with the separation of 'CuCl") as well as the precipitation phase of the remaining Cu ⁺ in

Solution Al® metallic copper in two stages or steps carried out are β 3) IEA allows the production of two types of cement copper, of which an arsenic-rich and a arseBfrei is that "both are returned to the first or" at the second reduction stage. From thus, the latter can be obtained arsenfraies _s CuCl the äbgemt and is processed in metallisclies copper "

jf

This Ai / i ^ itswai® © is s @ ixr complicated ₉ because it consists of four Yerfal'ireasstiii'sia Im H-slhe ₉ which, among other things , have to be balanced against each other and brought into equilibrium, and has the laeirfesilj that 'itself results in a product that weMea processes further. In addition, the solutions freed from copper contain, in addition to the Pe ^+, _{all of the ArSeB 5} initially present in the solution, a fact _{9 which} makes the purification of the solution all the more necessary, regardless of whether the others are present in it Metals to be extracted or not.

These working methods are absolutely tied to the necessity to make the copper insoluble as copper-I-chioxide, ie to convert the copper into a copper-I-chloride with a low * Cl / Cu-molar ratio in solution, which is necessary for the precipitation of CuCl is favorable. The solutions resulting from chlorinating volatilization generally have fairly high levels of chloride, which makes it rather difficult to obtain CuCl.

A 3-step process has now been used to obtain a cement-based copper with a high copper content and free of arsenic Arsenic-containing copper solutions found. . ·

The starting solutions are made from iron minerals or ores

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by chlorinating roasting or by chlorinating volatilization obtain. They contain copper ions, chlorine, arsenic, non-iron metal ions (such as Zn, Pb, Ag, Au, Mn, Co) and possibly iron ions and sulfate.

According to this method, an iron (II) salt (stage 1) is added to the solution so that the molar concentration of the le ⁺⁺ ions becomes equal to that of Cu ions, and then with a neutralizing agent (stage 2) to a pH of 3 to 3.5 brought. This results in a practically copper-free precipitate and a solution which, after filtration, is practically arsenic-free and contains all of the copper in monovalent form. This solution becomes quantitative of the precipitation. subjected or cemented, whereby a cement copper with high copper content is obtained, which is free of arsenic (stage 3).

An embodiment of this method is illustrated in the accompanying drawing.

In stage 1, part of the solution D, which flows out of the cementation stage 3 and contains Pe ⁺⁺ and other ions, is added to the starting solution A in such an amount that the molar concentration of the 3Pe ⁺⁺ ions in the resulting solution B is added the molar concentration of the Gu ⁺⁺ ions is equal to or slightly greater than this. The [Pe ^++] / [Cu ⁺⁺ 3-nis proportionality is to order the dilution to prevent the copper, a value of 1.1, preferably, not exceed ·, the solution A, a can ferrous salt in a concentrated solution or can also be added in the solid state, for example as the waste. 'product FeSO. 7Η ₂ 0.

In stage 2, the solution S is continuously mixed with CaCO, in .Pil preform or as a slurry with a high solids content (more than 500 g / ltr.) In one or more (preferred

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, wise two) reactors at a temperature between 20 and

! 8O ⁰ C, but preferably above 50 ⁰ C, and with a total of j

'Treatment times of 60 to 90 minutes treated in such a way that

, in the last reactor kept the pH between 3 and 3.5

ι will.

'. The neutralization of the solution to this value can be carried out in whole or in part with any basic substance available, in particular with products obtained in the course of the hydrometallurgical treatment itself, such as Pe (OH), which is obtained by removing the iron j is obtained from the solution after cementation (if it is necessary to extract other elements such as Co or Zn), '

ί Levels 1 and 2 can be performed simultaneously - using one; Salt or a mineral (for example siderite) are carried out, which is able to simultaneously neutralize the solution to the required pH and ^{to deliver the necessary Pe ++} in the solution.

ι In stage 2 the following reactions take place:

]? e + Cu ⁺⁺ _c Pe ⁺⁺⁺ + Cu ⁺

Cu ⁺ + 2Cl " _f (CuCl ₂ )

Pe ⁺⁺⁺ + 30ΙΓ> ()

The complete reduction of the Gu ⁺ * to the monovalent form is made possible by the iqtjivaXeaz occurring between Pe and Cut and, i by the precipitation of the Fe ⁺ * as hydroxide. ;

The monovalent copper is complexed by the Cl- ions and remains as a complex ion (CuCl ₂₎ "in solution · The zinc in the solution as a complex ion (ZnQl,)" "front. · The concentration of the chlorinating mud sufficient to both

ORIGINAL INSPECTED

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Ou ⁺ as well as Zn ⁺ " ⁴ * to bind complex, ie, it mtteeen-at least 1.166 g / Ltr. Cl""per 1 g / Ltr. Gu ⁺ and 2.17 g / Ltr. Cl" * per 1 g / Ltr. Zn ⁺⁺ are present.

It is preferable to work with an excess of $ 5 to $ 20 over the stoichiometric amount. If the concentration of solution B of Cl "falls below the fixed value, the addition of an alkali metal or alkaline earth metal fluoride is necessary, for example NaCl, OaCl ₂ , solution 1 after removal of Fe, solution D after removal of Fe uni Zn

In step 1, both the concentration of Fe ⁺⁴ "as well as the concentration of Cl" _{can be corrected at the same time by adding FeGl 2} (pickling solution with HCl or a solution obtained from the waste product FeSO. + CaCl ₂ ),

If the solution is carried out under suitable conditions (temperature, door and contact times), the conversion is almost quantitative. . .. iron hydrate also calcium Ti | ₁ .fat OaSCL "2HgQ. In addition, the precipitation of the arsenic in the form of iron arsenite, which is included in the cake, also takes place in this stage. The greater the initial Fe / As ratio of the solution, the more effective the precipitation of the arsenic is and is thus favored by the addition of Fe ⁺⁺ , which has been made for the reasons mentioned above.

After filtering (this step is labeled 2a in the drawing), the solution C obtained in this way is continuously cemented (step 3), working with an excess of iron (in the form of chips, scrap, foam, powder) and the flow in this way is regulated so that the complete cementation of the copper is achieved. This working step is carried out at a temperature between 20 and 40 ^° C., but preferably at room temperature, with contact times of 10 to

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Performed 20 minutes and preferably in the absence of air, "examples ■ Bpieleweiee in an atmosphere of 00g or N _{2> s} which can dae CO ₂ are from the leutralisationsphaee-" The reaction sequence is as follows:.! -

2 Cu ⁺ + Pe '—— ■■ ¥ 2 Cu- + ⁺ " ^} "

:, -: Vö'si a very small f © lineage des fe with Ie and H ge = · - iiiS of the entrance TbeselirieTbeaoa Eeaktionen can react ₀ The 'ferfersneli at Ilsen it shows Bich as something bigger than the

Ie per 1 "

After the separation of wqm i @ ® cement, solution D proves to be practically free from 6m Bii. Ai laai. contains a molar amount of? e ⁺⁺ j which is somewhat larger than € i © lol amount of copper In 3jö = smng C. A ffsil amount for LOsmiag B tena ^ as ready® he mentioned, on stage 1 resjkllai © ^ UQ ^ äeSp so '

of the molar Sonzentratioäea % u ± mh®m I © maä Ow ^ ⁺ in fi @ r resulting solution B gleiela "© S © 2? © fe7 © sg ^ oigr is al © in Stu

Sine JUteraative su der Harstellmiag v © m B © aQQ'5ioaj5ifo2 is ti © production of 1saeis <sh.em Kup £ ercM.orId

In this case, a fempemttiE ton 20 to 40 Cj ₁ is added to the solution, preferably at RaTömteeperatiiarp beioiaeii '^;

pH- ¥ ert swiBchen 5 ₉ 4 and 5 »8 air blown in. Let the amount used in this work piece be one. Excess of 20 to 30 $ over the fttr of the osydatlon chlorometrically researched amount _o larca fllie l'Jirkaag tion increases see the pH of the Ia8 © usg Ο ■ from äem ΙΊθζΊ 3 Ibis 3 »5 to the value tob © tea 5 and ulrä <äü , SB Ie of sodium hydroxide sßf ioa U @ st vosi S ₉ 4 Ils 5 _O

009883/156

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Under such conditions there is precipitation of copper as a basic chloride almost completely.

The fundamental advantage of the method according to the invention lies in the possibility of obtaining a cement copper with a high copper content (over 90 #), "which is arsenic-free (the Arsenic content is below 0.02 -. #), Through direct cementation in a single stage and with an iron consumption, which is half the size of what has been normal in industry up to now. ■

Another advantage lies in the fact that the copper-depleted solutions do not contain As and have a Pe ⁺ " ¹ " content which is low
solutions from industrial plants,

of Pe lower than that of similar ones

The problem of removing these substances, both in terms of the possible extraction of other valuable elements as well as being harmful in terms of disposal is therefore very much reduced.

Further advantages are also:

The reduction of copper from bivalent copper to monovalent Copper is made using SO «or metallic Copper by means of a cheap iron (II) salt in almost stoichiometrically isohem Scope carried out.

The cementation of copper is among better due to the absence of arsenic and therefore the absence of arsine Working conditions carried out. *

Duron is the cementation in an inert atmosphere Formation of hydroxides and basic iron salts, for example Pe (OH) CIp, which reduce the copper content of the cement.

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put, avoided.

During the cementation, energy losses occur "which are lower than with known methods, due to the absence - ■ of Pe ⁺⁺⁺ and the lower concentration of H ⁺ , ie the higher pH value.

The precipitation of the basic copper chloride by means of -BUft causes wedge
that would have to.

does not cause the formation of Fe ⁺⁺ ions, which are then eliminated

As a result of the return of the _{solution D, which also contains CaGl 2 in} addition to Pe, also Gl "° ions, which are useful for the formation of (CuClg)" and (ZnCl.) "* ~ Complexes, and Ca- Ions introduced by precipitation of SCh """" ions as calcium sulfate.

The following examples are intended to explain the invention further. but not limit.

example 1

In the event of chlorinating volatilization of lyric ash, an aqueous solution ^η "is obtained from the scrubber column for the volatile chlorides, which has the following composition (in g / l):

Za = 50.2 Pb = '0.85 AQ ₄ "*" * "= 31.5 Cu = 21.8 Ca = 0.89 Cl" = 142.5 Pe = 12.8 Mh = 0.16
As = 4.5 Co = 0.14

Ag = 0.01

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Iron (II) sulfate heptahydrate (24 kg / hour) is continuously added to solution A (at a flow rate of 1 m ^ / hour), whereby the concentration of iron and SO. Ions have a value of 17.7 or 39.8 g / ltr. achieved. The resulting solution B shows a molar concentration ratio of [Fe ⁺⁺ ] / [Cu ⁺⁺ ] of 1.026. Solution B is fed continuously into the first of two reactors arranged in cascade. In the first reactor, a metering valve is also an aqueous suspension of Kalksteda with a torch. Feeding speed of 800 g / hour. inaugurated. The pH of the slurry of the second reactor is maintained by a pH meter controlled and first by regulating the addition of limestone in de "reactor at 3.4» Neutralization (level 2) is at a! Temperature between 55 times 6Q ⁰ G in © iaer O.Qg atmosphere with continued stirring ■ at- “one” -g-esamtbertihrtuageeeit -the slurry in cts of 1 hour

läoh filter »in« latu ⁶ y \, imosptiBsn virü olac Warne Q received (1. m ^ / sti.), AiB lie JjI ^ w ¹ * "" v: ^ 3ootaimg (la g / ltr.) has:

Zn β 45.0 Ib * 0.38 30 ^ "" * = 1.20 Cu «20.7 Ca = 18.8 _οχ - _{= Q} .Ie« 0.28 m = 0 _f 15

As = 0.03 - Co = 0 _f 12

Ag = 0.007

The cake (120 kg! Dry weight) is then _{washed with water (60 liters) with a pH of 3 f} 5, which is maintained by adding HCl. The wash water contains 3.54% of the starting copper and 8.5% of the starting zinc and is then passed aurttek into the oil chloride scrubber column. At this stage the output copper is distributed in the following way:

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solution O 95 _f O2? ί. /

washed material 1.43? 6

The solution C coming from the neutralization stage (1 nr / hour) is placed in a continuous cementation device with a free volume of 0.25 m, the Egg scraps in large excess over that to be cemented Copper contains »The cementation is carried out at tree temperature and in a COg atmosphere with the solution in the cementation device of 15 minutes.

This gives 21.6 kg / h of cement which contains 94.5 % copper and 0.014 # arsenic. The cementation gives a yield of 98.5 56 and an iron consumption of 0.463 kg per 1 kg of copper produced.

Solution D (1 nr / hour) has the following composition (in g / ltr.) *

Zn = 44 , 80 Pb = 0.055 so - = 1.18 Cu s 0,
Pe = 9, 30th
72 Ca = 18.8
Ag = 0.00002 01 " = 134.5 As = 0, 00015 Mn = 0.15 Co = 0.12

In an Xest carried out in the same way, solution C (1 m / h) is continuously fed into a reactor. Air is blown through the reactor bottom in an excess of 25 % to precipitate the basic copper chloride. The oxidation is carried out at room temperature at a pH of 5.6 (which is maintained by adding 3 to 3.5 kg / h. Na ₂ CO *) with a residence time of the solution in the reactor of 60 minutes.

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This is 67.60 kg / hour, basic copper chloride with a copper content of $ 97 and with a yield with regard to the removal of the copper from the solution of. $ 95> received. The flowing solution can be subjected to normal conditions for the extraction of other metals (Co, Ni, Zn).

B is ρ ie 1 2 .

A plant for the chlorinating volatilization of pyrite ash becomes a solution A with the following composition (in g / Ltr ^ -) get:

Zn = 46.2 Pb = 0.76 ^s ° 4 ~ "~ = 33.56

Cu = 24.82 Ca »0.29 ' _C1 - -149.2

Ee = 16.59 Mn = 0.18

As = 4.86 Co = 0.15

= 0.03

The solution A (flow rate 1 m / hour ») are continuously 0.310 m / hour. mixed with a solution coming from the subsequent cementation. The resulting solution B shows a molar concentration ^{ratio of [Fe ++} ] / [Cu ⁺⁺ ] equal to 1.005 and has the following composition (in g / ltr.):

Zn = 44.8 Pb = 0.59 ^S0 4 ~ "= 25.90

Cu = 19.0 Ca = 5.50 _C1 - _{= 1 + 6 g}

Fe = 14.3 Mn = 0.17

As = 3.7 Co = 0.14

Ag = 0.024

₄ Solution B flows continuously into the first of two reactors arranged in cascade, into which an aqueous limestone suspension is also conveyed through a measuring valve

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800 g / ltr. is fed in. A pair of electrodes regulate the admixture of limestone in the first reactor so that the slurry of the second reactor has a pH of 3.3. The neutralization is carried out with stirring at a temperature between 55 and 60 ⁰ C with a total residence time of the slurry in the reactors of 1 hour,

By filtering the slurry in a COp atmosphere a solution (1.3 nr / hour) is obtained with the following composition shows:

SO ₄ "" = 1.16 Cl "* 138.5

Zn = 40, 3 Pb = 0.24 Cu = 17, 90 Approx = 22.50 Pe = ο, 25th Mn = 0.16 As - ο, 015 Co = 0.13 Ag = 0.016

The cake is washed according to the same procedures as described in Example 1. Contains the wash water, the # 4.8 of the starting copper and 8.0 f> of the starting zinc, is zurttckgeleitet in the -Scrubber column for chlorides. The copper is distributed as follows (in #, based on the starting copper):

► ■ ■ ^: - ■

Solution C 94.10 %

Washing water 4.80 #

washed material 1.10 #

Solution C coming from the neutralization stage (1.3 m / h) is introduced into a continuous cementation device with a free volume of 0.325 m, in which the Scrap iron is kept constant in large excess over the amount of copper to be cemented. The cementation takes place at room temperature with a residence time of the solution in

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the ZeMentation device ran for 15 minutes.

18.75 kg of Ztaent with a copper content of 94.2 % and 0.016% aria are triaged. The yield of tenets is 98.5 * at tinta Bietnrerbrauoh ron 0.492 kg per kg of cemented copper,

The outflowing solution D has the following composition (in g / ltr.):

Zn * 40.0 Pb = 0.026 S O ₄ ^ = 1.15 Cu = 0.25 • Approx »22.3 ₀ 1 "* 138.0 Fe - 6.93 Ag * 0.0004 As “0.0003 Mn = 0.163 Co * 0.129

From this solution, 0.31 w? returned to stage 1 to ^{correct the ratio [Pe ++} 3 / [Cu ⁺⁺ ] «u, while the remainder is sent to subsequent hydrometallurgical operations for the extraction of other elements.

Example 3

A solution A with the following Susana solution (in g / l) is obtained from the scrubber column of a plant for chlorinating volatilization of pyrite ash:

= 27.2 -154.0

Zn = 81.5 Pb = 0.82 SO, Cu s 30.0 Ca = 0.51 Cl * Pe = 4.4 Mh = 0.15 As = 3.3 Co = 0.12 ig = 0.01

Solution A (flow rate 1 a ³ / hour) are continuously 0.6 mVh. a solution of CaCIg (with

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150 g / liter of Cl), obtained from a solution D after the removal of the metals, and 75.2 kg / h. Iron (II) sulfate heptahydrate added. In this way, a suspension B is obtained, the liquid part of which has a molar concentration ^{ratio of [Pe ++} ] / [Cu ⁺⁺ ] equal to 1.085 and has the following composition (in g / l):

Zn = 50.95 Pb = 0.512 OV = 145.0

Cu = 18.75, Mn = 0.094

Pe = 17.85 Co = 0.075

As = 2.06, Ag = 0.006

A suspension B is continuously fed into the first of two reactors and an aqueous limestone suspension is fed through a measuring valve fed in at 800 g / Ltr *. '

A pair of electrodes regulate the addition of the limestone to the first reactor so that the slurries from the second reactor have a pH of 3.2. The neutralization is carried out at a temperature between 55 and 60 ⁰ C with continuous stirring and with a total residence time of the slurry in the reactors of 1 hour.

After filtering the slurry in a CO ₂ atmosphere, a solution C (1.6 m / h) is obtained which has the following composition (in g / l):

Zn = 47.40 Pb = 0.26 SO. = 0.40

Cu = 17.78 Ca = 62.0 ^ - ^

Pe = 0.35 Mn = 0.084

As = 0.005 Co s 0.069

Ag = 0.005

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The cake is washed according to the same procedures as in Example 1. The wash water, which contains $ 4 of the starting copper and $ 6.5 of the starting zinc, is returned to the scrubber column for separation of the chlorides. The copper is distributed as follows (in #, based on the starting copper):

Solution C $ 94.8>

Wash water 4.0 #
washed material 1.2 #

Solution C coming from the neutralization stage (1.6 m / h) is introduced into a continuous cementation device with a free volume of 0.400 m, in which the Iron scrap constant in large excess over the amount to be cemented Amount of copper is held. The cementation takes place at room temperature with a residence time of the solution in the Cementation device held for 15 minutes.

18.54 kg of cement with a copper content of 94 »6 f> and 0.012 fd arsenic are obtained. The cementation yield is $ 98.6 with an iron consumption of 0.482 kg per kg of learned copper.

The outflowing solution D has the following composition (in g / ltr.): '

Zn = 47.20 Pb * 0.025 ^so a ~~ ^s °> 4 °

Ou = 0.23 Oa «62.0 _σι - ₌

? e = 5.63 Mn -'s 0.083

As = 0.004 Oo = 0.068

Ag = 0.0001

* ■■■ '....

The solution is then passed to subsequent working holes for the removal of iron and zinc in accordance with the state of the art. i7

009883/1569 ",, _iNS PEcrr _E D

Claims (1)

MZm ₉₂ "' 20324Π P A T E N T ANSPHt C H E 1. Process for the production of arsenic-free cement copper from acidic arsenic-containing solutions by chlorinating Roasting or obtained by chlorinating volatilization of iron minerals and especially pyrite ash have been, characterized in that one In a first stage, the starting solution A is mixed with an iron (II) salt, so that the molar concentration of the Ee ⁺⁺ ions is equal to or slightly greater than the molar concentration of the Cu ⁺⁺ ions, whereby a solution B is obtained, in a second stage, the solution B is adjusted to a pH between 3 and 3.5 with a neutralizing agent at a temperature between 20 and 80 ⁰ G and then filtered, the filtrate C being obtained, and cemented in a third step, the filtrate with an upper w excess of metallic iron at a temperature of 20 to 4O ⁰ C, which arsenic-free cement copper is obtained, and also arsenic-free solution D rejects. '2 * method according to claim 1, characterized in that that A FeSO, 7HgQ "is used in the first stage of the solution. 3. Procedure according to Anepruoh 1, daduroh marked, that a rope of the discarded solution D is added to solution A in the first stage, .- 18.- 009883/1569 originally inspected M / 11192 4. The method according to claim 1, characterized in that the solution B in the first stage has a molar ratio of Pe ⁺⁺ / Cu ⁺⁺ between 1 and 1.1. 5. The method according to claim 1, characterized in that that the solution B in the second stage with limestone neutralized. - 19 - 009883/1569 BATH ORIGINAL Blank page